Process for titling positive or negative photographic film

ABSTRACT

A method for titling negative or positive photographic film with a minimum of film base embossing comprising the steps of: A. PROVIDING A TITLING ELEMENT COMPRISING A POLYMERIC SUPPORT HAVING FIRST AND SECOND SUPPORT SURFACES AND COATED UPON SAID FIRST SUPPORT SURFACE, TO PROVIDE A PRINTING SURFACE, A LAYER COMPRISING PROLAMINE, FILM FORMING PROMOTER, PLASTICIZER AND PIGMENT; B. JUXTAPOSING THE PHOTOGRAPHIC FILM AND THE TITLING ELEMENT, THE PRINTING SURFACE OF THE TITLING ELEMENT BEING ADJACENT THE PHOTOGRAPHIC FILM; C. STRIKING THE SECOND SUPPORT SURFACE OF THE TITLING ELEMENT WITH HEATED TYPE TO BRING THE PRINTING SURFACE OF THE TITLING ELEMENT INTO CONTACT WITH THE PHOTOGRAPHIC FILM FOR A PERIOD OF TIME SUFFICIENT TO TRANSFER SELECTIVE PORTIONS OF THE PRINTING SURFACE HAVING THE CONFIGURATION OF THE HEATED TYPE TO THE PHOTOGRAPHIC FILM WITHOUT TRANSFER OF ANY PORTION OF THE POLYMERIC SUPPORT; AND D. WITHDRAWING THE PRINTING SURFACE OF THE TITLING ELEMENT FROM THE PHOTOGRAPHIC FILM TO LEAVE THE SELECTIVE PORTIONS OF THE PRINTING SURFACE ON THE PHOTOGRAPHIC FILM.

United States Patent Gerhardt f i [151 3,660,139 [451 May2, 1972 [541 PROCESS FOR TITLING POSITIVE OR NEGATIVE PHOTOGRAPHIC FILM [72] Inventor: James S. Gerhardt, Rochester, N.Y.

[73] Assignee:

22] Filed: June 15, 1970 211 Appl.No.: 46,449

Related u.s. Application um [63] Continuation-impart of Ser. No. 678,196, Oct. 26,

1967, abandoned.

[56] References Cited UNITED STATES PATENTS 2,501 ,495 3/ 1950 Carroll et a1 ..l56l234 X 2,236,521 4/1941 Coleman 2,948,626 8/1960 Sanders ..106/24 Eastman Kodak Company, Rochester,

Primary Examiner- Edward G. Whitby Attorney-Walter O. Hodsdon and Arthur L. Girard s7 ABSTRACT A method for titling negative or positive photographic film a. providing a titling element comprising a polymeric support having first and second support surfaces and coated upon said first support surface, to provide a printing surface, a layer comprising prolamine, film forming promoter, plasticizer and pigment;

b. juxtaposing the photographic film and the titling element,

the printing surface of the titling element being adjacent the photographic film;

c. striking the seeondv support surface of the titling element with heated type to bring the printing surface of the titling element into contact with the photographic film for a period of time sufficient to transfer selective portions of the printing surface having the configuration of the heated type to the photographic film without transfer of any portion of the polymeric support; and

d. withdrawing the printing surface of the titling ele'ment from the photographic film to leave the selective portions of the printing surface on the photographic film.

9 Claims, No Drawings with a minimum of film base embossing comprising the steps.

releasable vehicle is highly util r'kociissroiz' rlrf j 'm ve n Niicn'ivii PHOTOGRAPHIC uLM' This application' i's'a"contintiation in-part of U.S; .Pat. application Ser. No. 678,1'9Q6filed Oct'. 26 1967, n'owaba doned.

This invention relates to titling materialswhich'wil[,through the use of heated" type', print a" egendflcn' developed'photo atitling' material compri in a" transferable coatiiig on a thin polymeric su'p'isan which wilh upon being struck by heated" leg eridfon' either negatii/e or posi solvent action by standard cleaning solutiohs such as" trijchlo'roethylenm ete. and they are easily smeared b y human or mechanical handling. Other meth as that have been us'edin the past to provide identifying rha'rltson photpgraphie filins also have serious disadvantages; For exa'rnple stencils have been used for cutting numbers into the filni, but this procedure is cumbersome and'frequer't'tly produce'slacerations ofmemm. v 3

Recently a, material" for priiiting' on photographic mar has been developed which consists of a polymeric support coated with a waxy layer containing carbon. The carbon wax' layer makes a satisfactory transfer to'film" when struck with heated typebut the typed image must be protected by an overcoat to prevent smearing or dissolutioh in common cleaning s'ol ents.

it is thus apparerit that a need exists'for a method o'f printing on negative or transparent positive film utilizing material which does not readilysmear or smudge, which is eyerily pigmen'tedand which is deposited with a minimum of film base embossing. Such film printing material must further be insoluble 'in common film cleaning" agents and must not tr'a'risfer to the opposite side of thefil'rn' if the filrt't' is rolled I In accordance with the present ifivention, it has been found that a film titling material comprisirfga' thin polymeric support upon which there is coated a merit suspended in a heat in pro idirig' a method pe. lri such manh'er the for titling film by the use of heated ty pigment is transferred from the titlir igrhaterial to" the film. The

resultant printing. does not readily smear or smudge; it is sharp and evenly pigmented and is deposited withminimum film em-' Missing. The film titling material of the present invention does not transfer to the opposite side of the film if the film is rolled up and it is insoluble in commonly used film cleaning agents such as naphtha, methylchloroforrn, freoris," etc., but is solu-' ble in commonly available orgariic solyents so that misprints or errors may be easily corrected.

Thus, the present invention provides asuspension of a finely divided pigment in a prolatnirie rriixtur'e, which suspeiisiori is coated from an organic solvent o'mda support. The resulting element, when struck byheated type; will print a clear, legend on developed photographic filin or paper.

it is, therefore, one object of this invention to provide him titling material which will print a clear, readable legend on developed photographic 'film or paper.

It is a further object of this iri eittion to provide a printing element comprising a support coated with a siispe'nsion of a pigment in a heat sealing vehicle.

It is another object of this invention to provide processes for applying legends to processed film or paper by the use of heated type. y p

lt still a further object of this invention to provide processes for applying legends to processed film or paper whereby a pigment composition is transferred from a printing element to processed photographic filrn or paper.

irigat least two layers one layer being a polymeric support havinga'meltingpoint'above about400 F. andanother layer including prolamine, pigment, film-forming: promoter and plasticizer; i

The pr'ola'rniiie utilized in the composition of the invention may be"prolamine'derived-from gluten, meal or maize. Particular protein's'which are utilized in preparing the ink composition of the present invention include corn protein, e.g. zeinj wheat' protein and-the like. Although zeinis a preferred material, other" prolarnines which, in combination with 1,5. plasticizer ad film-forming" promoter, melt in the range of It is th'e'p'rola'mi'ne which apparently provides the characteris'ticswhich'make'the'marking process of this invention superior'to those of the prior art. Evaluation of a' large number of materials" including the wax-carbon products described briefly above indicates that the proteinaceous prolamin'e which'is' a homolog of gelatin and therefore highly compatible with gelatin provides the properties which give the transfer materials of this invention their improved adhesion to positive or negative photographic materials; Without this improved compatability which permits the prolarnine layer applied to the gelatin coated photographic material to, so to speak, am alganiate with the gelatin'layer, the titling applied to the photographic film would smear and be'easily removed as in the case ofthe prior art materials.

This compatability of prolamine with gelatin is particularly evident in the case where the gelatin is a processed photo graphic emulsion of the type generally'present in conventional photographic positive or negative materials.

lnaddition to thepr'olamine, the binder for the pigment also contains small amounts of a film-forming promoter to assure afirm coating that does n'ot'easily rub off and to assure a uniform image transferl This promoter must,'of course, be compatible with the prol'amine andis usually selected from materials such as poly(vinyl' alcohol), slightly hydrolyzed poly (vinyl alcohol), cellulose nitrate, etc. v

The ratio of the prolamine, e.g. zein, to the film-forming promoter, e.g. low viscosity nitrocellulose, is important since the high film-forming properties of nitrocellulose will cause a ragged transfer of the printing medium unless the correct proportionisutilized. conventionally a ratio of .l( )+2:l, zein to nitrocellulose, utilized. A ratio of 4:1, zeintonitrocellulose,

produces highly beneficial results. By increasing or decreasing the ratio of plasticizer to' the corn protein, the heat sealing range of the composition can be varied.. I,

The selection of the plasticizer utilized in the preparation of the ink of the present invention is important since, the plasticizer must not be soluble in the commonly used solvents utilized during film cleaning. The plasticizer must, however, be soluble in certain conventional solvents so that the ink may be eradicated in the event of misprint or error. A plasticizer usuallyutilized is an alkyl acid phthalate including straight chain alkyl and cycloalkyl acid phthalates. Typical plasticizers include such compounds as d imethyl phthalate, diethyl phtha= late, dibutyl phthalate, dicyclohexyl phthalate and the like. A

. preferred plasticizer is a cycloalkyl acid phthalate such as cyclohexyl acid phthalate. Also polyalkylene glycol plasticizers such as-Carbowax 400, Carbowax 700, etc. and glycol ethers, e.g. diethylene glycol, etc., may be used together with or in lieu of the phthalate plasticizers. The plasticizer prolamine ratio advantageously is about 2-lzl.

The pigments utilized in the compositions of the present invention are those materials usually utilized in printing inks,-

, e'.g. such materials as a titanium oxide, e.g. titanium dioxide and various forms of carbon such as carbon black, Dixon graphite, zinc oxide and the like. The ratio of pigment to the vehicle in which it is suspended, e.g. zein, hitrocellulose and plasticizer is also important since the resultant image is very thin. There must be sufficient pigment transferred from the titling element to form easily readable images. The ratio of invention may be ethyl alcohol, e.g. 95% ethyl alcohol,

isopropyl alcohol, etc. The concentration of the pigment and vehicle in solvent may be dictated by standard coating techniques but the solvent usually amounts to about half the total weight of the coating solution. I i

The thin polymeric base over which the ink suspension is coated is selected so that the heat of the type will release the ink cleanly from the base. Suitable components for the thin polymeric support include polyesters such as polyethylene terephthalate and cellulose organic esters including cellulose propionate, cellulose acetate, cellulose acetate propionate, cellulose acetate-butyrate, cellophane and the like. The support should have a thickness of about 0.0005 to about 0.002 inch in order that the tape will be heated quickly by the type when transferring the ink suspension to the film. In addition, the support may be coated by materials which will facilitate the'heat release and stabilize the resultant image to an even greater degree. The transfer from the coated polymeric support can be .made to either the emulsion or the support side of photographic film or paper. The photographic support is, of course, not critical and many examples are conventionally known in the art.

The pigment suspension is coated onto the thin support from a solvent at a thickness of from about 0.0005 to about 0.00 l 5 inch.

The titling element of the present invention which as just described comprises a polymeric support having first and second support surfaces, the first supportsurface being coated with a layer comprising prolamine, film forming promoter, plasticizer and pigment to provide a printing surface is utilized according to the process ofthe present invention by:

l. juxtaposing the photographic film and-the titling element, I theprin ting surface of the titling element being adjacent the photographic film striking the second support surface of the titling element with heated type to bring the printing surface of the titling element into contact with the photographic film for a period of time sufficient to transfer selective portions of the surface having the configuration of the heated type to v the photographic film without transfer of any portion of the polymeric support; and

3. withdrawing the printing surface of the titling element from the photographic film to leave the selected portions of the printing surface on the photographic film.

The type may be, for example, electrically heated type having a temperature between about 250 and 350 F and preferably between about 300350 F. The striking of the printing element of the invention by the heated type thus transfers the pigment suspension from the thin polymeric support to the photographic film which is to be titled.

The invention will be more fully illustrated by the following examples.

EXAMPLE 1 A suspension of finely divided graphite ina heat sealing adhesive vehicle is prepared from the following materials:

Ethanol (95%) The suspension is coated on a 0.0015 inch thick poly( ethylene terephthalate) support. The solvent is evaporated leaving a firm, uniform coating on the support. This material is then Ethanol(95%) EXAMPLE 2 1 A suspension of finely divided graphite in a heat sealing adhesive vehicle is prepared from the following materials:

.. pl... by Weight Components Zein 8.5' Cyclohexyl acid phthalate [5.0 Graphite 25.0 I Nitrocellulose, V4 second ss. 3.0 53.0

The suspension is coated on a 0.0015 inch thick 'cellulose acetate support. The solvent is evaporated leaving a firm.

uniform coating on the support. This material is then utilized with heated type to print legends on photographic film. The legends are easily readable, stable to cleaning solutions and relatively smudge free.

EXAMPLE 3 'the following materials:

Components Parts by Weight Zein 20.0 Cyclohexyl acid phthalate 35.0 Nitrocellulose, V4 second ss. v y 7.5- Dixon graphite (200-39) 650 Ethyl alcohol The suspension is coated ona 0.0015 inch thick cellulose acetate propionate support. The solvent is evaporated leaving EXAMPLE 4 A suspension of finely divided graphite is prepared from the following components:'

Components Parts by Weight Zein 8.0 Carbon 20.0 Cyclohexyl acid phthalate 5.0 Carbowax 400 14.0 Ethyl alcohol (95%) 48.0 Silica smoke 4.2

The suspension is coated on a 0.00l5 inch thick cellulose acetate butyrate' support. The solvent is evaporated leaving a firm, uniform coating on the support. This material is then utilized with heated type to print legends onphotographic film. The legends are easily readable, stable to cleaning solutions and relatively smudge free. i

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove.

l. A method for titling negative or positive photographic film having a surface comprising a layer of gelatin, with a minimum of film base embossing, comprising the steps of:

a. providing a titling element comprising a polymeric support having first and secondsupport surfaces and coated uponsaid first support surface, to provide a printing surface, a layer comprising prolamine, film forming promoter, plasticizer and pigment;

b. juxtaposing the photographic film and the titling element, the printing surface of the titling element being adjacent said layer of gelatin;

I c. Striking the second support surface of the titling element 2. The method of claim l wherein-said support has a thickness of from about 0.0005 to about 0.002 inch.

3. The method of claim 2'wherein said heated type are at a temperature of between about 250 and 350 F.

4. The method of claim 1 wherein said prolamine is com protein.

5. The method of claim 1 wherein said prolamine is zein 6. The method of claim 5 wherein the film forming promoter is low viscosity cellulose nitrate and at least one plasticizer is cycloalkyl acid phthalatel 7. The method of claim 6 wherein the zein cellulose nitrate ratio is in the range of about 10-2: 1.

8. The method of claim 7 wherein the zeincellulose nitrate weight ratio is about 4:1.

9. The method of claim 8 wherein the zein cycloalkyl acid phthalate ratio is about l:l-2 and the type is heated to a temperature of between about 300and 350 F. 

2. The method of claim 1 wherein said support has a thickness of from about 0.0005 to about 0.002 inch.
 3. The method of claim 2 wherein said heated type are at a temperature of between about 250* and 350* F.
 4. The method of claim 1 wherein said prolamine is corn -protein.
 5. The method of claim 1 wherein said prolamine is zein.
 6. The method of claim 5 wherein the film forming promoter is low viscosity cellulose nitrate and at least one plasticizer is cycloalkyl acid phthalate.
 7. The method of claim 6 wherein the zein - cellulose nitrate ratio is in the range of about 10-2:1.
 8. The method of claim 7 wherein the zein - cellulose nitrate weight ratio is about 4:1.
 9. The method of claim 8 wherein the zein - cycloalkyl acid phthalate ratio is about 1:1-2 and the type is heated to a temperature of between about 300*and 350* F. 